1. 1 Envir Chem at KMUTT-JGSEE – Jun. –Sept., 09 Time: Location: http://www.unc.edu/courses/2009fall/enst/430/001/ Rich Kamens; kamens@unc.edu http://www.unc.edu/~kamens/

2. 2 u Textbook u Environmental Chemistry by Colin Beard and Michael Cann, ISBN > ISBN-13 978-1-4292- 0146-0, publishers W.H. Freeman and Company, New York, 773 pages, 2008

3. 3 Who is Richard Kamens u Professor of Atmospheric chemistry and teach graduate classes in Environmental chemistry u Direct a smog chamber research group u Focus on aerosol formation in the atmosphere u Direct a student exchange program between UNC and Thai Universities

4. 4 UNC outdoor chamber

5. 5 Gas/Particle partitioning of toxics organics on different aerosols

6. 6 New UNC Aerosol Smog Chamber

7. 7 Dual 270m 3 chamber fine particle t 1/2 >17 h

8. 8 We generate models to predict organic aerosol formation in the atmosphere from smog chamber experiments u Numerical fitting u Semi-explicit

9. 9 Link gas and particle phases C=O O cis-pinonaldhyde particle C=O O Gas phase reactions

10. 10 [ i gas] + [part] [ i part] [ i gas] + [part] [ i part] K p = k on /k off k on k off particle k on k off C=O O

11. 11 CHO O O CH 3 O O O Criegee2 Criegee1 O O O  -pinene O 3 COOH pinic acid + other products O pinonic acid CHO O COOH + CO, HO 2, OH COOH O norpinonaldehyde norpinonic acid Mechanism

12. 12 pinonaldehyde

13. 13 Overall kinetic Mechanism u linked gas and particle phase rate expressions

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15. 15 Chemical System  -pinene + NOx+ sunlight + ozone----> aerosols

16. 16 0.95 ppm  -pinene + 0. 44ppm NO x O3O3 NO NO 2 model data Time in hours EST ppmV

17. 17 Gas phase pinonaldehdye O O mg/m 3 Time in hours EST

18. 18 Particle phase model TSP mg/m 3 Particle phase model TSP mg/m 3 Measured particle mass vs. model data Time in hours EST

19. 19 UNC outdoor chamber group

20. 20 The Thai-CEP Undergraduate/Graduate Exchange Program Pollution does not understand boarders. We must begin to address these problems from both inside and outside ones culture.

21. 21 General Approach u Since 2001, UNC-CEP undergraduates participated in a 6+ month experience in Thailand that begins at the end of May 2001 u Small groups of UNC students come together with Thai students to study and work on a research project at various Thai universities. u Thai students will go back with UNC students for a semester at UNC.

22. 22 Classes UNC students take 3 direct contact/web- based environmental classes u Atmospheric and ecotoxicology u LCA u Energy and the Environment u Climate Change and Eco u Biomass and Energy u Energy and the Environ

23. 23 Feasibility of Ethanol Use and an Energy Analysis and Environmental Impact of Ethanol in Thailand: KMUTT 2001- 2002

24. 24 The Feasibility of Bio-diesel Production as Petroleum Substitute in Thailand : KMUTT 2004 Energy balance Used vegetable oil Production from Jatropha

25. 25 Water Quality Report: Mae Kha Canal & Ping River: CMU, Chiang Mai, 2004

26. 26 Air Pollution in Northern Thailand

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33. 33 Long standing relationship with Peking University and CRAES Since 1983 there were 13 visiting Chinese scholars in our research group at UNC

34. 34 Introduction to Environmental Physical Organic Chemistry Environmental chemistry may be defined as "the study of sources, reactions, transport, effects, and fates of chemical species in water, soil, and air environments, and the effects of technology thereon.” Manahan, 1994

35. 35 Class objectives: Highlight some important areas in environmental chemistry present some of the common techniques that environmental chemists use to quantify process that occur in the environment u It is assumed that everyone has courses in organic and physical chemistry.

36. 36 Class objectives: u We will cover general topics: Global warming, Strat. O3, aerosols, photochemical smog, acid rain, etc. u Develop relationships will be used to help quantify equilibrium and kinetic processes

37. 37 Thermodynamics u u i = u o 1 +RT ln p i /p * iL  f i =  i Xi p i * pure liquid u RT ln f i hx /f i o pure liq = RT lnf i H2O /f i o pure liq f i hx = f i H2O  ln K p = a 1/T+b

38. 38 Vapor pressure How to calculate boiling points

39. 39 Vapor pressure and Henry’s law K P C PV iaw i iw sat iL * iw  Solubility and activity coefficients Octanol-water partitioning coefficients

40. 40 Homework, quizzes, exams u There will be example homework exercises; These types of questions will appear on exams.

41. u There are more than 100,000 synthetic chemicals that are in daily use: –solvents –components of detergents –dyes and varnishes –additives in plastics and textiles –chemicals used for construction –antifouling agents –herbicides, insecticides,fungicides Why the interest?

42. u Polynuclear Aromatic HC (PAHs) u Dioxins u Ketones u PCBs u CFCs u DDT u O 3, NO 2, aerosols, SO 2 Some examples of environmental chemicals

43. u Formed from small ethylene radicals “building blocks” produced when carbon based fuels are burned u Sources are all types of burning u in ChiangMai, Thailand: a) 2-stroke motorcycle engines b) cars- light diesels c) open burning d) barbecued meat?? PAHs

44. 44 Combustion Formation of PAH Badger and Spotswood 1960

45. u Metabolized to epoxides which are carcinogenic; O PAH u are indirect acting mutagens in bacterial mutagenicity tests (Ames- TA98+s9) u methyl PAHs are often more biologically active than PAHs PAHs

46. u Professor Gernot Grimmer extracted different types of smoke particles u He then took the extract and applied it to mouse skin u and implanted it into rat lungs u How did he obtain extracts? u How did he fractionate his extracts?? Carcinogenic tests with PAHs

47. 47 u Extraction by soxhlet extraction starts with solvent (MeCl 2 ) in a flask

48. 48 u Extraction by soxhlet extraction starts with solvent (MeCl 2 ) in a flask MeCl 2

49. 49 u The solvent is heated and starts to evaporate Heat

50. 50 u Evaporated solvent goes into a water cooled condenser where hot solvent drips out Heat

51. 51 u The hot solvent drips into another glass chamber that contains the filter. Heat sample

52. 52 u Hot solvent fills this chamber and bathes the filter Heat

53. 53 u The solvent in the filter chamber then drains back into the heated flask with chemicals from the particles on the filter Heat

54. 54 u The organic liquid in the soxhlet flask can be concentrated by evaporation by a dry nitrogen stream or rotary evaporation u the extract can then be fractionated into different polarity compound groups

55. 55 Professor Grimmer fractionated the exhaust extracts

56. 56 Professor Grimmer fractionated the exhaust extracts HPLC column (silica gel)

57. 57 Professor Grimmer fractionated the exhaust extracts HPLC hexaneMeCl 2

58. 58 Professor Grimmer fractionated the exhaust extracts HPLC hexaneMeCl 2 uv or fluorescence detector

59. 59 Professor Grimmer fractionated the exhaust extracts HPLC Total extract hexaneMeCl 2 uv or fluorescence detector

60. 60 Professor Grimmer fractionated the exhaust extracts HPLC PAH 2 &3 rings Total hexane uv or fluorescence detector

61. 61 Professor Grimmer fractionated the exhaust extracts HPLC Total PAHs> 3 rings hexaneMeCl 2 uv or fluorescence detector

62. 62 Professor Grimmer fractionated the exhaust extracts HPLC Total Total -PAHs uv or fluorescence detector ACN

63. 63 Professor Grimmer fractionated the exhaust extracts HPLC PAH 2 &3 rings Total PAHs> 3 rings Total Total -PAHs uv or fluorescence detector

64. 64 u skin painted mice u implanted rat lungs What did Grimmer see when exposed rats and mice to the different fractions?

66. Total minus the PAH fraction

69. u These are some of the most toxic organics in the environment - LD 50 u Created by burning organics which have chlorine; incineration is a big source of atmospheric dioxins and furans u bleaching in making paper is another source Chlorinated dibenzo dioxins and Furans

70. 70 Combustion Formation of Dioxins from Polychlorinated phenol OH Polychlorinated Phenol Flame OH.. O OH Cly + O OH + OH Chlorinated dibenzo dioxin Cl x O O Shaub & Tsang, ES&T 1983. Cl y Cl x Cl y Cl x

71. They have the following general structures O O Cl x y chlorinated dioxin

72. They have the following general structures O O Cl x y chlorinated dioxin O Cl x y chlorinated furan

73. u The most toxic is either the 2,3,7,8 tetrachlorodibeno dioxin and furans More than 200 different structures are possible O O Cl

74. u These types of compounds produce toxic enzymes: arylhydrocarbon hydroxylase and 7-ethoxyresorufin deethylase u At low concentrations they may behave as environmental estrogens

75. u Environmentally, they are unreactive and can be transported long distances u They did not start to show up in the environment until the 1920s when there was a big increase in the production of chloro-organics (Professor Ron Hites, and students)

76. 76 Environmental Fate of Chlorinated Dioxins and Furans (Czuczwa and Hites, 1984) u Collected core sediment samples from southern Lake Huron in the USA  Based on sedimentation rates they established age vs. concentration profiles for chlorinated dioxins and furans

77. 77 US coal consumption vs chlorinated aromatic production

78. 78 Chlorinated aromatic production vs dioxin and furan conc. in lake core samples

79. u used as coolants - insulation fluids in transformers, capacitors, plastercisers, additives to epoxy paints u are thermally stable and biologically stable u can exist in the gas and particle phases Polychlorinated biphenyls (PCBs)

80. 80 Cl y x PCB structures u Environmentally, they used to be considered unreactive, but there is evidence for some bio-degradation; they can be transported long distances

81. 81 What do we do now, when new compounds are introduced into the environment...?? u toxicity?? u low concentration health effects? u damage to the ecosystem ? u where will it show up in the environment? u how is it transported in the environment and what is its life- time?

82. Some examples of environmental exposures

83. 83 1. There is a general concern that if we observe abnormalities in wildlife, similar kinds of mechanisms may exist in humans.

84. 84 Mercury poisoning off the coast of Minamata, Japan is an example u Fishermen in the 1950s noticed sea birds were dying and feral cats that scavenged fish from the docks were “stiff legged” (see page 675 Baird and Cann,2008)  Cerebral palsy and mental retardation started showing up in children.

85. 85 2. Toxic loads u Scientists have hypothesized that the fetus is sharing the mother’s toxic load, and may actually provide some protection to the mother by reducing her internal exposure.

86. 86 2. Toxic loads u Children get 12% of their lifetime exposure to dioxins during the 1st year. u Their exposure is 50 times greater than an adult during a very critical developmental period.

87. 87 2. Toxic loads u Firstborns from dolphins off the coast of Florida usually die before they separate from their mothers

88. 88 2. Toxic loads u It is speculated that mother dolphins unload 80% of their accumulated pollutants into their calves, probably during nursing. u The greatest exposures occurs with the 1st born u Does this have any implications for humans?

89. 89 3. Pesticide exposures u Children of farm families in the western Minnesota area of the US have significantly higher rates of birth defects than the general population. u The highest rates are among children conceived in the spring when spraying of pesticides is most intense; male babies had far more birth defects than females

90. 90 4. The end points may not only be cancer, but compromised immune systems and generally poorer health.

91. 91 4. Immune systems & Mother’s milk u In the Netherlands researchers have found that children with higher levels of dioxins and PCBs in their bodies have more health problems (immune system and hormonal changes) than children with lower levels. u This was linked to levels of PCBs in Mother’s milk.

92. 92 4. Mother’s milk u Mother’s milk from Inuit Indians in the Canadian Arctic has 7 times the PCBs as mother’s milk from women in the urban industrialized areas of southern Quebec.

93. 93 4. Mother’s milk u During the first year, Inuit babies suffer through 20 times more colds than babies in southern Quebec. u Acute ear infections are rampant.

94. 94 4. Mother’s milk u Babies nursed by mothers with the highest contamination levels in their milk are afflicted with more acute ear infections than bottle fed Inuit babies. u Many of these children don’t seem to produce enough antibodies for childhood vaccinations to take.

95. 95 5. PCBs and lower intelligence u There is evidence of lower intelligence in babies exposed to PCBs. u In adults, a blood-brain barrier insulates the brain from many potentially harmful chemicals circulating through the body u In a human child this barrier is not fully developed until 6 months after birth.

96. 96 5. PCBs and lower intelligence u In 1979 in Taiwan, more than 2000 people were exposed to PCB- contaminated cooking oil. u In the 1 st 3 months many babies died outright. As the surviving children grew up, many were slower intellectually than other kids their age, were hyperactive and had behavioral problems.

97. 97 5. PCBs and lower intelligence u Similar observations were made in "high-PCB kids" in the Lake Michigan area. u This was associated with mothers eating salmon and trout from the Lake during the years before their children were born.

98. 98 5. PCBs and lower intelligence u At age 4 the high exposure group had poor short term memories. At age 11 the 30 most highly exposed kids had average IQ scores that were 6 points lower than the lowest-exposed group. u biomarker-metabolites???

99. 99 7. Sexual impairment u There is evidence for sexual impairment in both animals and humans from high PCB exposures and other environmental chemicals. u Male beluga whales in the very polluted St. Lawrence River have exhibited female organs.

100. 100 7. Sexual impairment u Highly exposed humans, alligators and panthers exhibit smaller male sex organs and low sperm counts. u Testicular cancers have nearly doubled among older teenagers in the US between 1973 and 1992. u In previous lectures I have said these have been linked to toxic exposures....long way from finding proof.

101. 101 7a. Sexual impairment u In a new study (Hardwell et al, Environ Presp, 2003) woman who’ve had substantial exposure to certain environmental pollutants are more likely to bear sons who develop testicular cancers (men ~ 30 years of age) u From 1973-1999 testicular cancers up 67% u Men with test-cancers had high cis nona chloridane, not PCBs, etc u Mothers, however, had high PCBs, HCB (hexa- chlorobenzenes) and cis nona chloridane

102. 102 7b. Sexual impairment u These same mothers probably had high exposures when environmental contaminates peaked in Scandinavia in the 1970s u Richard Sharpe of Edinburogh and Niels Skakkebek (Denmark) proposed that exposure to endocrine disruptors before birth can alter testicular-cell development and some of these cells may be cancerous after puberty. u This may also may explain rising rates of male infertility, and other sexual deformities

103. 103 8. Endocrine disrupters u These studies have led to the notion of environmental "endocrine disrupters". u In the lock and key relationship between hormone and receptor molecules, these "hormone impostors" can:

104. 104 8. Endocrine disrupters u bind with receptors and trigger biological processes u or bind with receptors and tie up an active hormone site u Some of these have been called environmental estrogens

105. 105 9. Other chemicals u From a historical perspective, everyone is now carrying at last 250 measurable chemicals that were not part of human chemistry before the 1920s (Peter Myers, 1996) u The most basic toxicity testing results cannot be found in the public record for nearly 75% of the top volume chemicals in commercial use in the USA

106. 106 9. Other chemicals u In other words, the public cannot tell whether a large majority of the highest-use chemicals in the United States pose health hazards or not (Amicus Journal, p23, Spring 1998). u An example are phthalates that go into many types of plastics which have been shown to reduce the sperm counts in mice.

107. 107 9. Other chemicals u Bisphenol-A (BPA) is an additive in polycarbonate plastics used in food liners, dental sealants, and dental fillings. u BPA causes increased prostate size in mice exposed to tiny doses while in the womb. These doses were 25,000 times smaller than the EPA threshold.

108. 108 9. Phthalates u Exposure of female rates to 200 to 1000 mg/kg body weight results in much lower testosterone in male offspring ( L. Earl Gray. Jr. EPA, RTP, J. Tox and Ind. Health, Mar, 1999). u Exposures to the herbicide linuron made the epididymis (sperm-storing organ in rats) is much smaller in male rats.

109. 109 epididymus

110. 110 Recommendations u During the insecticide spraying season, farmers should not try to have children. u Limit exposures to pesticides around the home. u When possible, buy foods that were grown without pesticides. u Governments must try to limit PCB introduction into the environment. u If incineration is used, chlorinated plastics should be removed, along with modern technology.